JP6690934B2 - Underwater photorefractive display and manufacturing method thereof - Google Patents

Description

  The present invention relates to an underwater photorefractive display and a method for manufacturing the same. More specifically, the present invention relates to an underwater photorefractive display body in which the display portion is different in air and water and a manufacturing method thereof.

Conventionally, there has been disclosed a color-changing laminate in which a porous layer having different transparency in a liquid-absorption state and a non-liquid-absorption state in which hydrophobic silica is fixed to a binder resin in a dispersed state is provided on a support (for example, See Patent Document 1).
The discolorable laminate does not discolor even when water adheres, and when a liquid having a specific interfacial tension value adheres to the porous layer, it becomes transparent due to liquid absorption, and the color and image of the lower layer can be visually recognized. In addition, the present invention is applied to applications in which a color other than water is used for discoloration, and applications where it is not discolored in water, regardless of the weather and place of use.
Apart from this, the appearance seen in the air and the appearance seen in water are different, and as an attempt to add variability, the picture drawn is put in a transparent bag and immersed in water. An invisible underwater magic card is disclosed (for example, see Non-Patent Document 1).
In the underwater magic card, the picture is visually recognized in the air through the air inside the bag and the transparent bag, but when immersed in water, the picture becomes invisible because the transparent bag and the water have a close refractive index.
Although the underwater magic card can add fun such that the picture visible in the air is not visible in the water, it takes trouble to put the picture in a transparent bag and it does not change when water enters the bag Could occur.

JP, 2014-124908, A

Simple physical experiment and physical toys DataBase "Let's make an underwater magic card", [Online], [Search on December 11, 2014], Internet <URL: http://www.info-niigata.or.jp /~ymiyata/others/magic/magic.htm>

  SUMMARY OF THE INVENTION The present invention is intended to provide an underwater photorefractive display body and a method for manufacturing the same, in which the display portion in air and water is different.

In the present invention, a water-repellent display portion is provided on a surface of a support, wherein hydrophobic silica is fixed to an organic solvent-soluble resin in a dispersed state, and the mass ratio of the hydrophobic silica and the organic solvent-soluble resin is 1: 2. to 1: 5, the interfacial tension value of the water repellent display is 0 mN / m or more, 50 mN / m less than der is, and, between the support and the water repellent display unit, an organic solvent-soluble hydrophobic silica A water-repellent reinforcing layer fixed to a resin in a dispersed state is provided, and the content of the hydrophobic silica contained in the water-repellent reinforcing layer is 3% or more lower than the content of the hydrophobic silica contained in the water-repellent display part. A photorefractive display is required.
Furthermore, the supporting bearing member surface, and hydrophobic silica, and an organic solvent, a liquid composed of an organic solvent-soluble resin was printed or painted, the water-repellent reinforcing layer provided by removing the organic solvent, the water-repellent reinforcing A method for producing an underwater photorefractive display element, in which a hydrophobic silica, an organic solvent, and a liquid material composed of an organic solvent-soluble resin are printed or coated on the layer to remove the organic solvent and provide a water-repellent display part, As a requirement.

  INDUSTRIAL APPLICABILITY The present invention can provide an underwater photorefractive display body and a method for manufacturing the same, in which it is possible to easily visually recognize different display portions in air and water.

It is a longitudinal section explanatory view of one reference example of the underwater optical refraction indicator of the present invention. It is a longitudinal section explanatory view of one example of the underwater optical refraction indicator of the present invention.

The underwater photorefractive indicator of the present invention is provided with a water repellent indicator in which hydrophobic silica is fixed in a dispersed state in an organic solvent-soluble resin on the surface of a support.
The material of the support is not particularly limited, and examples thereof include paper, synthetic paper, knit, woven fabric, non-woven fabric, synthetic leather, leather, plastic, metal, glass, ceramics, wood, stone and the like.
The shape of the support is not particularly limited, and may be a plane shape, a sheet shape, or a shape having a curved surface or unevenness.
A colored layer containing a colorant may be provided between the support and the water repellent display portion.

Next, the hydrophobic silica contained in the water repellent display portion will be described.
Silica is classified into a dry method and a wet method depending on the manufacturing method, and both have a structure in which silanol groups are arranged on the surface.
Hydrophobic silica reacts silanol groups with silanes such as methylchlorosilane, siloxanes such as polydimethylsiloxane, and hexamethyldisilazane to change the hydrophilicity of silanol groups to hydrophobic, so that it cannot absorb water. Shows water repellency.
As the general-purpose hydrophobic silica, trade name Nipsil SS-10, SS-20, SS-70, SS-40, SS-50, SS-100, Nippon Aerosil Co., Ltd., manufactured by Tosoh Silica Co., Ltd. Company name AEROSIL R972, RY50, R812, R805, RX200, RY200, Cabot Carbon Co., Ltd. product names TS-530, TS-610, TS-720, Degussa Japan Co., Ltd. products Name AEROSIL R202, same R805, same R812, trade name REOLOSIL MT-10, same DM-10, same DM-20S made by Tokuyama Corporation, product name SYLOPHOBIC100, same 200, same 704, same made by Fuji Silysia Chemical Ltd. 4004, 507, 702, 505, 603 and the like.
The hydrophobic silica has a refractive index in the range of 1.4 to 1.8.
The particle size of the hydrophobic silica is not particularly limited, but a particle size of 0.03 to 10.0 μm is preferably used. For the particle size measurement, a laser diffraction / light scattering type particle size distribution measuring device (LA-300 manufactured by Horiba Ltd.) or a dynamic light scattering type particle size distribution measuring device (SZ-100 manufactured by Horiba Ltd.) is used.
The hydrophobic silica may be used in combination of two or more kinds.

The hydrophobic silica is dispersed in a solvent containing an organic solvent-soluble resin to prepare a liquid material such as a paint or a printing ink, and a printing method such as screen printing, offset printing, gravure printing, coater, tampo printing, and transfer. The water repellent display portion is provided on the surface of the support by a method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating and dip coating.
Since it is difficult to disperse the hydrophobic silica in a water-based emulsion as well as in an aqueous emulsion by an ordinary method, the hydrophobic silica is used by being dispersed in an organic solvent.
The organic solvent-soluble resin is dissolved or dispersed in an organic solvent, and a liquid composition containing hydrophobic silica is coated on a support in whole or in part and dried to obtain an underwater photorefractive display.
The organic solvent-soluble resin is a resin that dissolves at 5% by weight or more in an organic solvent at 30 ° C.

  Examples of the organic solvent include n-paraffin solvents, isoparaffin solvents, naphthene solvents, aromatic solvents, petroleum solvents such as α-olefin solvents, light oil, spindle oil, machine oil, cylinder oil, turpentine oil, Mineral spirits, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate, xylene, toluene, ethanol, isopropyl alcohol, butanol and the like can be mentioned.

Examples of the organic solvent-soluble resin include urethane resins, acrylic ester resins, acrylic ester copolymer resins, acrylic polyol resins, vinyl chloride-vinyl acetate copolymer resins, maleic acid resins, polyester resins, styrene resins, styrene copolymers. Resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, casein, starch, polyvinyl alcohol, urea resin, Phenolic resin, acrylic resin, polyester resin, alkyd resin, styrene resin, nylon resin, vinyl acetate resin, vinyl chloride resin, acrylonitrile-butadiene-styrene copolymer resin, Loin resins.
The mixing ratio of the hydrophobic silica and the organic solvent-soluble resin depends on the type and properties of the hydrophobic silica, but is preferably 2 to 5 parts by mass of resin solid content relative to 1 part by mass of the hydrophobic silica, More preferably, it is 2 to 3.5 parts by mass. When the resin solid content is less than 2 parts by mass with respect to 1 part by mass of the hydrophobic silica, it is difficult to obtain a practical film strength of the water-repellent display part formed, and when it exceeds 5 parts by mass. Reduces the amount of the hydrophobic silica oriented on the surface of the water-repellent display portion, and makes it difficult to exhibit the photorefractive effect in water.
In the water-repellent display part, since the mixing ratio of the organic solvent-soluble resin to the hydrophobic silica is small as compared with a general coating film, it is difficult to obtain sufficient film strength. Therefore, it is preferable to increase the scratch resistance by using a nylon resin, a urethane resin, or an acrylic resin among the organic solvent-soluble resins.
Examples of the urethane-based resin include polyester-based urethane resin, polycarbonate-based urethane resin, and polyether-based urethane resin, and two or more kinds of them can be used in combination.
The urethane-based resin may be used alone, or may be used in combination with another binder resin depending on the type of the support and the performance required for the film.
In the organic solvent-soluble resin, a crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent to effect crosslinking.
The organic solvent-soluble resin includes a resin having a dry dry film and a resin having a hydrophilic dry film. Preferably, when a resin having a dry dry film is used, the photorefractive effect in water becomes large.
Further, since the organic solvent-soluble resin imparts water repellency to the film after drying, it is preferable to use a fluororesin or a silicone resin alone or in combination. By using the resin, the addition amount of the hydrophobic silica is relatively small. At least a light reflection effect in water can be exhibited.
A colorant may be contained in the water repellent surface portion.

The water-repellent display portion of the underwater photorefractive display element has an interfacial tension value of more than 0 mN / m and more than 50 mN / m.
When the interfacial tension value is 50 mN / m or more, the affinity for water becomes high and the underwater photorefractive effect becomes difficult to be exhibited.

  The underwater photorefractive display element obtained as described above, when immersed in water, an air layer is formed between the water and the water repellent display surface due to the air in the pores of the hydrophobic silica, Depending on the angle of view from the difference in the refractive index of light, light refraction occurs at the interface between the water and the air layer, causing a phenomenon that reflects like a mirror, causing a different appearance from that in air (a silver color that was not visible in air. The reflected light is visible. The point of the present invention is to dispose hydrophobic silica on the surface of the water repellent display portion.

Further, between the support and the water-repellent display portion, a water-repellent reinforcing layer having hydrophobic silica fixed to an organic solvent-soluble resin in a dispersed state is provided, and the content of the hydrophobic silica contained in the water-repellent reinforcing layer is By lowering the content of the hydrophobic silica contained in the water repellent display portion by 3% or more, it is possible to prevent the water repellent display portion from cracking.
If the water-repellent display portion is directly provided on the support, cracking is likely to occur. This is because the water-repellent display part formed by applying a water-repellent display part ink comprising a hydrophobic silica, an organic solvent-soluble resin and an organic solvent on a support by a method such as painting or printing Due to convection in the display part and thixotropy as a viscosity characteristic due to evaporation of the organic solvent, it becomes difficult to flow and it becomes a water repellent display part from both phenomena of convection and attempting to dry without maintaining smoothness. It is considered that cracking is likely to occur.
Upon studying the improvement of the cracks, a water-repellent reinforcing layer containing the same hydrophobic silica as that of the water-repellent display portion was provided between the support and the water-repellent display portion, and the hydrophobic silica contained in the water-repellent reinforcement layer was contained. By making the ratio 3% or more lower than the content of the hydrophobic silica contained in the water repellent display portion, cracking is less likely to occur as compared with the above-mentioned system in which the water repellent display portion is provided on the support.

  The underwater photorefractive indicator is provided with a water-repellent indicator by printing or coating a liquid material composed of hydrophobic silica, an organic solvent, and an organic solvent-soluble resin on the surface of the support and removing the organic solvent. A method for production, or by printing or coating a liquid material comprising hydrophobic silica, an organic solvent, and an organic solvent-soluble resin on the surface of the support, removing the organic solvent to provide a water repellent reinforcing layer, It can be obtained by a manufacturing method in which a liquid material composed of hydrophobic silica, an organic solvent, and an organic solvent-soluble resin is printed or coated on the reinforcing layer, and the organic solvent is removed to provide the water repellent display portion.

The underwater photorefractive display is an underwater toy, a toy imitating a ship or a submarine, an underwater game product, an underwater decoration product, a pseudo bait for fishing, a display for underwater work such as diving, an ornamental fish tank decoration tool, Used for swimwear.
As the underwater decorative article, the underwater photorefractive display body is obtained by attaching an underwater photorefractive display body having a water repellent display section to a plastic molded body having a curved surface to the movable section and operating the movable section in water. An example is a decorative article that is activated and the water-repellent display part becomes invisible due to refraction of light without changing the viewing angle, and the silver reflected light is visually recognized.
Examples of the movable portion include a motor and an air pump. Examples of the movable portion include a configuration in which the underwater photorefractive display body is rotated by using a motor, and the underwater photorefractive display body is moved by air using an air pump.

Examples will be described below, but the present invention is not limited to these examples.
The parts in the examples are parts by mass.
Method for measuring interfacial tension value The interfacial tension on the surface of the water-repellent display part was measured according to the JIS K6768 wet tension test method.
Method for measuring refractive index of hydrophobic silica It was measured by a liquid immersion method (Becke line method) using a contact liquid (refractive liquid) manufactured by Shimadzu Corporation.

Reference example 1 (see Figure 1)
Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS20] 9.8 parts, vinyl chloride-vinyl acetate copolymer resin as organic solvent-soluble resin (Nisshin Chemical Industry Co., Ltd., product name Solvain C solid (100%), 20 parts of cyclohexanone, 50 parts of cyclohexanone, and 1 part of a nonionic additive were mixed to obtain an ink for a water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 2.04).
A circular water-repellent display part 3 was provided by screen printing using a water-repellent display part ink on a blue cast coated paper having a thickness of 100 μm as a support 2 to obtain an underwater photorefractive display part 1.
The interfacial tension on the surface of the water repellent display part was 45 mN / m.
In the underwater photorefractive display body, a light blue circular water-repellent display portion was visually recognized on the blue base material in the air, and the circular water-repellent display portion was always visually recognized even when the viewing angle was changed.
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the circular water-repellent display portion which had been visually recognized became invisible due to the refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive display was taken out of water, the circular water-repellent display was always visible, and the appearance change could be repeated.

Reference example 2
Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 2 parts, red pigment (Clariant Co., Ltd., product name HOSTAPERM RED D3G) 0.05 part, solvent type fluorine resin as organic solvent soluble resin (DIC Corporation, product name Defencer TR-101 solid content 31%) 10 parts, cyclohexanone 2 parts, isocyanate-based curing agent (manufactured by DIC Corporation, product name Vernock DN-950 solid content 75%) 2 parts, 1 part of a nonionic additive was mixed to obtain an ink for a water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 2.3).
A water-repellent display was obtained by providing a striped water-repellent display by screen printing using a water-repellent display ink on a 100 μm thick transparent polyethylene terephthalate film as a support. The interfacial tension on the surface of the part was 39 mN / m.
In the underwater photorefractive display member, a light red striped water repellent display portion was visually recognized on a transparent support in the air, and the striped water repellent display portion was always visually recognized even when the viewing angle was changed. .
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the striped water-repellent display portion which had been visually recognized disappeared due to the refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of the water, the striped water-repellent display was always visible, and the appearance change could be repeated.

Reference example 3
2.3 parts of hydrophobic silica [manufactured by Tosoh Silica Co., Ltd., product name Nipseal SS50A], 0.05 part of blue pigment (Clariant Co., Ltd., product name HOSTAPERM BLUE B2G), solvent-type acrylic as an organic solvent-soluble resin An ink for a water-repellent display part was obtained by mixing 10 parts of a resin [manufactured by DIC Corporation, product name: Acridic A-801-P solid content 50%] and 20 parts of butyl acetate (hydrophobic silica and organic solvent soluble). Resin solids ratio, 1: 2.2).
A water-repellent display for water was obtained by providing a heart-shaped water-repellent display by spray coating using a water-repellent display ink on a white ABS plate as a support.
The interfacial tension on the surface of the water repellent display part was 39 mN / m.
In the underwater photorefractive display body, a light blue heart-shaped water-repellent display portion was visually recognized on a transparent support in the air, and the heart-shaped water-repellent display portion was always visually recognized even when the viewing angle was changed. .
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the heart-shaped water-repellent display portion, which had been visually recognized, became invisible due to refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of water, the heart-shaped water-repellent indicator was always visible, and the appearance change could be repeated.

Preparation of ink A for water-repellent display part 2 parts of hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A], blue pigment [Clariant Co., product name HOSTAPERM BLUE B2G] 0.05 part, organic As a solvent-soluble resin, a solvent-type fluorine-based resin [DIC Corporation, product name Defencer TR-101 solid content 31%] 20 parts, butyl acetate 20 parts, isocyanate-based curing agent [Asahi Kasei Co., Ltd., product name Duranate 24A -100 solid content 100%] 1.7 parts were mixed to obtain an ink for a water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 4.0).
Preparation of ink B for water-repellent display part 2.3 parts of hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A], blue pigment [Clariant Co., product name HOSTAPERM BLUE B2G] 0.07 part , Solvent type fluorine resin [DIC Corporation, product name Defencer TR-101 solid content 31%] 20 parts, butyl acetate 20 parts, isocyanate type curing agent [Asahi Kasei Co., Ltd., product name Duranate 24A-100 solid Min. 100%] 1.7 parts was mixed to obtain an ink for a water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 3.4).
Preparation of ink C for water-repellent display part Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 2.7 parts, Blue pigment [Clariant Co., product name HOSTAPERM BLUE B2G] 0.08 part , An organic solvent-soluble resin, a solvent-type fluororesin [manufactured by DIC Corporation, product name Defencer TR-101 solid content 31%] 20 parts, butyl acetate 20 parts, an isocyanate curing agent [manufactured by Asahi Kasei Co., Ltd., product name Duranate 24A-100 solid content 100%] 1.7 parts was mixed to obtain an ink for water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 2.9).
Preparation of Ink D for Water-Repellent Display Part Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 3.3 parts, Blue pigment [Clariant Co., product name HOSTAPERM BLUE B2G] 0.1 part , An organic solvent-soluble resin, a solvent-type fluororesin [manufactured by DIC Corporation, product name Defencer TR-101 solid content 31%] 20 parts, butyl acetate 20 parts, an isocyanate curing agent [manufactured by Asahi Kasei Co., Ltd., product name Duranate 24A-100 solid content 100%]) was mixed to obtain an ink for a water-repellent display portion (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 2.4).

Production of Underwater Photorefractive Display A white ABS plate as a support was spray-coated with the inks A to D for the water-repellent display in the constitutions shown in the following Tables and Reference Examples 4 to 9 and Examples. The underwater photorefractive indicators of Examples 1 to 4 were obtained.
The water-repellent display portion inks A and B in Reference Example 8 and Examples 1 to 4 are provided as water-repellent reinforcing layers.
In Reference Example 9 , a white ABS plate was coated with a clear ink prepared by mixing 10 parts of a 50% butyl acetate solution of acrylic resin and 20 parts of butyl acetate, and then an ink D for a water-repellent display part was applied to the water-repellent display part. The photorefractive indicator for underwater was obtained by providing.

The evaluation contents of each examination item in the table are as follows.
Underwater photorefraction test Observe the fabricated underwater photorefractive body in the air at different angles to see if the reflecting surface (mirror surface) is visible.
Next, the underwater light refracting body is immersed in water and the angle is changed in the same manner as in the air to observe, and it is confirmed whether the reflecting surface (mirror surface) can be seen.
⊚: Good photorefractive property is shown, and the reflection surface (mirror surface) is visually recognized.
◯: Shows light refractivity and the reflection surface (mirror surface) is visually recognized.
●: A reflective surface (mirror surface) that has practicality is visually recognized although the optical refraction is slightly low.
Appearance (Crack) Test The presence or absence of cracks in the appearance (water repellent display part) of the underwater photorefractive indicator was confirmed.
⊚: No external cracks are found.
◯: Practicality is satisfied although there are slight cracks in the appearance.
●: The appearance is cracked, but it is practical.
Adhesion Test An adhesive tape is attached to the water-repellent display part of the underwater light refracting body under a load of 500 g, and peeled off at an angle of 60 ° to confirm the peeling of the water-repellent display part (coating film).
A: No peeling of the water-repellent display part was observed.
◯: Peeling is observed in the water-repellent display part, but the practicality is satisfied.

Reference example 10
Nine parts of hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A], 40 parts of an acrylic resin (DIC Co., Ltd., product name Acridic A-166 solid content 45%) as an organic solvent-soluble resin, cyclohexanone 20 parts and 1 part of a nonionic additive were mixed to obtain an ink for a water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 2.0).
On a blue polyester satin fabric as a support, a star shape is printed by screen printing using the ink for the water-repellent display portion, heated at 120 ° C. to remove the organic solvent, and the water-repellent display portion is provided to provide a water-repellent display portion. A photorefractive display was obtained.
The interfacial tension on the surface of the water repellent display part was 40 mN / m.
In the underwater photorefractive display element, a light blue star-shaped water-repellent display portion was visually recognized on a blue base material in the air, and the star-shaped water-repellent display portion was always visually recognized even when the viewing angle was changed.
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the star-shaped water-repellent display portion that had been visually recognized disappeared due to refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of water, the star-shaped water-repellent indicator was always visible, and the appearance change could be repeated.

Reference example 11
Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS20] 5 parts, hydrophobic silica [Fuji Silysia Chemical Co., Ltd., product name SYLOPHOBIC100] 5 parts, vinyl chloride-vinyl acetate copolymer as organic solvent soluble resin 20 parts of resin (manufactured by Nissin Chemical Industry Co., Ltd., product name Solvain C solid content 100%), 20 parts of cyclohexanone, 5 parts of butyl acetate and 1 part of nonionic additive are mixed to obtain an ink for a water-repellent display part. (Hydrophobic silica and organic solvent soluble resin solid ratio, 1: 2).
On the hemispherical red ABS resin as a support, the letter "P" was printed by tampo printing using the water-repellent display ink and left at room temperature for 1 day to evaporate the organic solvent, A water repellent display portion was provided to obtain an underwater photorefractive display member.
The interfacial tension on the surface of the water repellent display part was 45 mN / m.
In the underwater photorefractive display body, the water-repellent display portion of the light red "P" character is visually recognized on the red base material in the air, and the water-repellent display portion of the "P" character is always visible even if the viewing angle is changed. Was seen.
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the water repellent display portion of the "P" character that had been visually recognized became invisible due to the refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of the water, the water repellent display portion of the letter "P" was always visible, and the appearance change could be repeated.

Example 5 (see FIG. 2)
2.3 parts of hydrophobic silica [manufactured by Tosoh Silica Co., Ltd., product name Nipseal SS50A], 0.07 part of blue pigment [manufactured by Clariant Co., Ltd., product name HOSTAPERM BLUE B2G], solvent type fluorine resin [DIC ( Co., Ltd., product name Defencer TR-101 solid content 31%] 20 parts, cyclohexanone 10 parts, isocyanate curing agent [Asahi Kasei Co., Ltd. product name Duranate 24A-100 solid content 100%] 1.7 parts are mixed. Thus, an ink for a water-repellent display portion was obtained (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 3.4).
Heart-shaped printing is performed on the pink vinyl chloride sheet as the support 2 by screen printing using the ink for the water-repellent display portion, and then heated at 60 ° C. to evaporate the organic solvent to reinforce the water-repellent property. Layer 4 was provided.
Next, hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 2 parts, blue pigment [Clariant Co., Ltd., product name HOSTAPERM BLUE B2G] 0.05 part, solvent type as an organic solvent soluble resin Fluorine-based resin [DIC Corporation, product name Defencer TR-101 solid content 31%] 20 parts, cyclohexanone 10 parts, isocyanate-based curing agent [Asahi Kasei Corporation, product name Duranate 24A-100 solid content 100%] 1.7 parts and 1 part of a nonionic additive were mixed to obtain an ink for a water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 4.0).
Using the ink for the water-repellent display portion, heart-shaped printing is performed on the water-repellent reinforcing layer in the same size and shape by screen printing, and then heated and dried at 60 ° C. to obtain the water-repellent display portion 3. Was provided to obtain an underwater photorefractive display element 1.
The interfacial tension on the surface of the water repellent display part was 39 mN / m.
In the underwater photorefractive display body, a light purple heart-shaped water-repellent display portion was visually recognized on a pink substrate in the air, and the heart-shaped water-repellent display portion was always visually recognized even when the viewing angle was changed. .
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the heart-shaped water-repellent display portion, which had been visually recognized, became invisible due to refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of the water, the heart-shaped water-repellent indicator was always visible, and the appearance change could be repeated.

Reference example 12
Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 9 parts, blue pigment [Clariant Co., Ltd., product name HOSTAPERM BLUE B2G] 0.1 part, acrylic resin (DIC ( Co., Ltd., product name Acridic A-166 (solid content 45%) 40 parts, ethyl acetate 40 parts, and nonionic additive 1 part were mixed to obtain a water-repellent display ink (hydrophobic silica and organic solvent). Soluble resin solids ratio, 1: 2.0).
A polka dot pattern was printed by gravure printing on the transparent polyester film as a support using the ink for water-repellent display, and the organic solvent was removed by heating at 100 ° C. to provide a water-repellent display. An underwater photorefractive display was obtained.
The interfacial tension on the surface of the water repellent display part was 40 mN / m.
In the underwater photorefractive indicator, a light blue water-repellent display portion of a polka dot pattern was visually recognized on a transparent substrate in the air, and a water-repellent display portion of a polka dot pattern was always visually recognized even when the viewing angle was changed.
When the underwater photorefractive indicator was immersed in water and the viewing angle was changed, the water-repellent display portion with a polka dot pattern that had been visually recognized became invisible due to refraction of light, and silver reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of the water, the water-repellent indicator of the polka dot pattern was always visible, and the appearance change could be repeated.

Comparative Example 1
0.5 parts of hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A], 0.01 part of red pigment [Clariant Co., Ltd., product name HOSTAPERM RED D3G], solvent type fluorine as an organic solvent-soluble resin System resin [DIC Corporation, product name Defencer TR-101 solid content 31%] 10 parts, cyclohexanone 2 parts, isocyanate-based curing agent [DIC Corporation product name, Vernock DN-950 solid content 75%] 2 Parts and 1 part of a nonionic additive were mixed to obtain an ink for a display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 9.2).
A transparent polyethylene terephthalate film having a thickness of 100 μm was used as a support, and a striped display portion was provided by screen printing using the above-described ink for the display portion to obtain a display member.
The interfacial tension on the surface of the display part was 45 mN / m.
In the display body, the light red striped display portion was visually recognized on the transparent support in the air, and the striped water repellent display portion was always visually recognized even when the viewing angle was changed.
Even when the display body was dipped in water and the viewing angle was changed, the striped display portion was always visually recognized, and the phenomenon that the display portion was not visually recognized due to refraction of light did not occur.

Comparative example 2
Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 4 parts, red pigment [Clariant Co., Ltd., product name HOSTAPERM RED D3G] 0.1 part, solvent type fluorine resin as organic solvent soluble resin [DIC Corporation, product name Defencer TR-101 solid content 31%] 10 parts, cyclohexanone 2 parts, isocyanate-based curing agent [DIC Corporation, product name Vernock DN-950 solid content 75%] 2 parts, An ink for a display portion was obtained by mixing 1 part of a nonionic additive (solid content ratio of hydrophobic silica and organic solvent-soluble resin, 1: 1.2).
A 100 μm thick transparent polyethylene terephthalate film was used as a support, and a striped display portion was provided by screen printing using the above-described ink for a display to obtain a display.
The interfacial tension on the surface of the display part was 35 mN / m.
In the display body, the light red striped display portion was visually recognized on the transparent support in the air, and the striped water repellent display portion was always visually recognized even when the viewing angle was changed.
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the striped water-repellent display portion which had been visually recognized disappeared due to the refraction of light, and silver-colored reflected light was visually recognized.
Although the striped water-repellent display is always visible when the underwater photorefractive display is taken out from water, the adhesive test shows that the display can be easily peeled off with the adhesive tape to satisfy repeated use. I couldn't let you do it.

1 Underwater Photorefractive Indicator 2 Support 3 Water Repellent Display 4 Water Repellent Reinforcing Layer

Claims (2)

The support surface is provided with a water-repellent display part in which hydrophobic silica is fixed in a dispersed state in an organic solvent-soluble resin, and the mass ratio of the hydrophobic silica and the organic solvent-soluble resin is 1: 2 to 1: 5. , and the interfacial tension value of the water repellent display is 0 mN / m or more, 50 mN / m less than der is, and, the dispersion state between the support and the water repellent display unit, a hydrophobic silica in an organic solvent-soluble resin A water-repellent reinforcing layer fixed to the water-repellent reinforcing layer is provided, and the content of the hydrophobic silica contained in the water-repellent reinforcing layer is 3% or more lower than the content of the hydrophobic silica contained in the water-repellent display section. body. On the support surface, hydrophobic silica, an organic solvent, by printing or coating a liquid material consisting of an organic solvent-soluble resin, to remove the organic solvent to provide a water-repellent reinforcing layer, on the water-repellent reinforcing layer, The method for producing an underwater photorefractive display element according to claim 1, wherein a liquid material comprising hydrophobic silica, an organic solvent, and an organic solvent-soluble resin is printed or painted to remove the organic solvent to provide a water-repellent display portion. .

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